WO2012043617A1 - Composition d'huile lubrifiante pour réfrigérateur à compression - Google Patents

Composition d'huile lubrifiante pour réfrigérateur à compression Download PDF

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Publication number
WO2012043617A1
WO2012043617A1 PCT/JP2011/072162 JP2011072162W WO2012043617A1 WO 2012043617 A1 WO2012043617 A1 WO 2012043617A1 JP 2011072162 W JP2011072162 W JP 2011072162W WO 2012043617 A1 WO2012043617 A1 WO 2012043617A1
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Prior art keywords
oil composition
group
lubricating oil
carbon atoms
groups
Prior art date
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PCT/JP2011/072162
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English (en)
Japanese (ja)
Inventor
知也 松本
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出光興産株式会社
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Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to KR1020137007470A priority Critical patent/KR101837222B1/ko
Priority to US13/822,894 priority patent/US20130274163A1/en
Priority to CN201180043871.6A priority patent/CN103108944B/zh
Priority to EP11829170.7A priority patent/EP2623583B1/fr
Publication of WO2012043617A1 publication Critical patent/WO2012043617A1/fr
Priority to US14/931,879 priority patent/US10774252B2/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/04—Metals; Alloys
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/16—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/04—Well-defined cycloaliphatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/067—Unsaturated Compounds
    • C—CHEMISTRY; METALLURGY
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

Definitions

  • the present invention relates to a lubricating oil composition for a compression type refrigerator, and more particularly, to a lubricating oil composition for a compression type refrigerator having good thermal and oxidation stability using a saturated fluorinated hydrocarbon having a low carbon number as a refrigerant. It is.
  • saturated fluorinated hydrocarbons having 1 or 2 carbon atoms, which are refrigerants that do not destroy the ozone layer, are used in compression refrigerators such as air conditioners and car air conditioners.
  • compression refrigerators such as air conditioners and car air conditioners.
  • these compression refrigerators are increasingly used under harsh conditions for an extended period of time. Accordingly, a lubricating oil composition used for such a compression refrigerator is required to have excellent thermal and oxidation stability.
  • R32 difluoromethane
  • R410A and R407C mixed refrigerants
  • HFC refrigerants that do not destroy the ozone layer in various compression refrigerators including air conditioners.
  • R32 has been used as HFC refrigerants that do not destroy the ozone layer in various compression refrigerators including air conditioners.
  • R32 has a relatively high theoretical COP and heat transfer coefficient and a low pressure loss of the refrigerant, it has a characteristic of high energy efficiency when used in an air conditioner.
  • R32 has a characteristic that the discharge temperature of the compressor is about 20 ° C. higher than the conventional R410A and R407C. From such a situation, for example, research for improving the structure of the refrigeration apparatus as disclosed in Patent Document 1 has been performed.
  • a lubricating oil for a compression type refrigerator using these refrigerants a lubricating oil composition having high thermal and oxidation stability in the presence of those refrigerants is required.
  • saturated HFCs have high stability, and existing antioxidants used for R134a and the like It was thought that it was possible to cope with this problem by adding an acid scavenger. However, even when existing antioxidants and acid scavengers were simply blended, or when the blending amount was increased, the effect was low.
  • JP 2001-183020 A Japanese Patent Laid-Open No. 02-258896 Japanese Patent Laid-Open No. 02-289898 Japanese Patent Laid-Open No. 02-305893
  • the present invention is a compression type excellent in thermal and oxidation stability even when used in a compression type refrigerator using a saturated fluorinated hydrocarbon refrigerant having a low carbon number and a low global warming potential.
  • An object of the present invention is to provide a lubricating oil composition for a refrigerator.
  • the present inventors have achieved the object by including, as a stabilizer, an organic compound having a double bond in a specific molecule in the base oil. Found to get.
  • the present invention has been completed based on such findings. That is, the present invention
  • Lubricating oil composition for type refrigerator (6) The lubricating oil composition for a compression refrigerator according to (1), wherein the saturated fluorinated hydrocarbon having 1 to 3 carbon atoms is difluoromethane (R32), (7)
  • the refrigerant is a mixture of difluoromethane (R32) and pentafluoroethane (R125), or difluoromethane (R32) and pentafluoroethane (R125) and 1,1,1,2 tetrafluoroethane (R134a).
  • a lubricating oil composition for compression refrigerators according to (1), (8) The lubricating oil composition for a compression refrigeration machine according to (7), wherein the refrigerant is a refrigerant containing 20% by mass or more of difluoromethane (R32), (9)
  • the base oil is at least one selected from polyoxyalkylene glycols, polyvinyl ethers, poly (oxy) alkylene glycols or copolymers of the monoethers and polyvinyl ethers, polyol esters, and polycarbonates.
  • the lubricating oil composition for a compression type refrigerator according to any one of (1) to (11), wherein the base oil has a viscosity index of 60 or more
  • the composition further comprises at least one additive selected from an extreme pressure agent, an oily agent, an antioxidant, an acid scavenger, a metal deactivator, and an antifoaming agent.
  • the compression type refrigerator according to any one of (1) to (13), wherein the sliding portion of the compression refrigerator is made of engineering plastic or has an organic coating film or an inorganic coating film.
  • the organic coating film uses a polytetrafluoroethylene coating film, a polyimide coating film, a polyamideimide coating film, and a resin base material composed of a polyhydroxy ether resin and a polysulfone resin and a resin coating material containing a crosslinking agent.
  • the lubricating oil composition for a compression type refrigerator according to (14), wherein the inorganic coating film is any one of a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film, and a molybdenum film.
  • the lubricating oil for the compression refrigeration machine is excellent in thermal and chemical stability.
  • a composition can be provided.
  • the lubricating oil composition for a compression refrigerator of the present invention comprises a base oil, an organic compound having two or more non-conjugated double bonds in the molecule, a terpene compound having a double bond in the molecule, and a double in the molecule. And an organic compound having a double bond in the molecule, which is at least one selected from aliphatic unsaturated hydrocarbons having 12 to 30 carbon atoms having one bond.
  • Organic compound having double bond in molecule> Organic compounds having two or more non-conjugated double bonds in the molecule
  • Non-conjugated double bond means a relationship in which double bonds are separated by two or more single bonds. The double bond may or may not be included in the aromatic ring.
  • the number of nonconjugated double bonds is counted as two.
  • the number of non-conjugated double bonds contained in the molecule is 2 or more, preferably 4 or less, more preferably 3 or less, and particularly preferably 2.
  • the upper limit of the non-conjugated double bond is about 10.
  • Such an organic compound having two or more non-conjugated double bonds in the molecule preferably has a 1,4-diene structure or a bridged cyclic structure.
  • the 1,4-diene structure means a structure having double bonds at the 1-position and 4-position
  • the bridged cyclic structure means that the ring is divided into at least one ring.
  • Examples of the organic compound having a 1,4-diene structure include 1,4-cyclohexadiene, 2-vinyl-1-methylenecyclopropane, 1,3-dimethylenecyclobutane, 4-methylenecyclopentene, 2-methyl-1, 4-pentadiene, 1,4-hexadiene, 3-methyl-1,4-pentadiene, 3-methyl-1,4-cyclohexadiene, 1,4-cycloheptadiene, 3-vinyl-1,4-pentadiene, 2 , 5-heptadiene, 4-methylenecyclohexene, 5-methyl-1,4-hexadiene, 2,4-dimethyl-1,4-pentadiene, 1,4-cyclooctadiene, 2,3-dimethyl-1,4- Hexadiene, 3-methyl-1,4-heptadiene, 1,4,7-cyclononatriene, 1,3,5-trimethyl-1,4-cycl Hexadiene, (Z) -1,4
  • Examples of the organic compound having a bridged cyclic structure include 2,5-norbornadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 7-methyl-2,5-norbornadiene, 7-ethyl- 2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7- Dimethyl-2,5-norbornadiene, 7-methyl-7-ethyl-2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5- Norbornadiene, 1-butyl-2,5-norbornadiene, bicyclo [3.2.0] hepta
  • organic compounds having two or more non-conjugated double bonds in the molecule include 1,5-hexadiene, 1-methyl-1,5-cyclohexadiene, 3-methylene-1,5-hexadiene, 2-methyl -1,5-hexadiene, 4-methyl-1,5-hexadiene, 2-methyl-1,5-hexadiene, 3-methyl-1,5-hexadiene, 1,6-heptadiene, 1,5-heptadiene, 4 -Vinyl-1-cyclohexene, 1,5-cyclooctadiene, 1,4-bismethylenecyclohexane, 1,7-octadiene, 2,5-dimethyl-1,5-hexadiene, 3-ethyl-1,5-hexadiene 2,6-octadiene, 1,6-octadiene, 1-methyl-2,3-divinylcyclobutane, 1- (1-methylethenyl) -3-cyclohex 1-
  • Terpene compound having a double bond in the molecule As the terpene compound having a double bond in the molecule, isoprene dimers to octamers are preferable, and aliphatic unsaturated hydrocarbons, particularly ⁇ -pinene and ⁇ -pinene, are particularly preferable.
  • aliphatic unsaturated hydrocarbon having 12 to 30 carbon atoms with one double bond in the molecule The aliphatic unsaturated hydrocarbon having 12 to 30 carbon atoms having one double bond in the molecule is preferably an ⁇ -olefin having 12 to 30 carbon atoms.
  • 1-tetradecene, 1-hexadecene, 1- Examples include octadecene and 1-icosene.
  • a terpene compound having a double bond in the molecule is preferable, and pinene, particularly ⁇ -pinene is preferable.
  • the amount of the organic compound having a double bond in the molecule is preferably 0.1% by mass or more and 10% by mass or less based on the total amount of the composition.
  • the blending amount is more preferably 0.1% by mass or more and 5% by mass or less, and further preferably 0.1% by mass or more and 3% by mass or less.
  • the lubricating oil composition for compression refrigerators of the present invention only needs to contain an organic compound having a double bond in the molecule, and may contain other oxygen scavengers as necessary. .
  • the base oil in the present invention is at least one selected from polyoxyalkylene glycols, polyvinyl ethers, poly (oxy) alkylene glycols or copolymers of the monoethers and polyvinyl ethers, polyol esters, and polycarbonates. It is preferable that a seed is included as a main component.
  • polyoxyalkylene glycols examples include compounds represented by general formula (I).
  • R 1 -[(OR 2 ) m -OR 3 ] n (I) (Wherein R 1 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, or An oxygen-containing hydrocarbon group having 1 to 10 carbon atoms, R 2 is an alkylene group having 2 to 4 carbon atoms, R 3 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or carbon (The oxygen-containing hydrocarbon group having a number of 1 to 10, n is an integer of 1 to 6, and m is a number with an average value of m ⁇ n of 6 to 80.)
  • the monovalent hydrocarbon group having 1 to 10 carbon atoms in each of R 1 and R 3 may be linear, branched, or cyclic.
  • the hydrocarbon group is preferably an alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, Various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and the like can be mentioned.
  • the alkyl group When the alkyl group has more than 10 carbon atoms, the compatibility with the refrigerant is lowered, and phase separation may occur.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • the hydrocarbon group portion of the acyl group having 2 to 10 carbon atoms in each of R 1 and R 3 may be linear, branched or cyclic.
  • the hydrocarbon group portion of the acyl group is preferably an alkyl group, and specific examples thereof include the same various groups having 1 to 9 carbon atoms as specific examples of the alkyl group.
  • a preferred acyl group has 2 to 6 carbon atoms.
  • R 1 and R 3 are both hydrocarbon groups or acyl groups, R 1 and R 3 may be the same or different from each other.
  • n is 2 or more, a plurality of R 3 in one molecule may be the same or different.
  • R 1 is a hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites
  • the hydrocarbon group may be a chain or a cyclic one.
  • the hydrocarbon group having two bonding sites is preferably an aliphatic hydrocarbon group, for example, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, cyclopentylene group.
  • a lenylene group and a cyclohexylene group is preferably an aliphatic hydrocarbon group, for example, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, cyclopentylene group.
  • hydrocarbon groups examples include residues obtained by removing hydroxyl groups from bisphenols such as biphenol, bisphenol F, and bisphenol A.
  • the hydrocarbon group having 3 to 6 binding sites is preferably an aliphatic hydrocarbon group, for example, trimethylolpropane, glycerin, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane, 1,3,3.
  • residues obtained by removing a hydroxyl group from a polyhydric alcohol such as 5-trihydroxycyclohexane.
  • examples of the oxygen-containing hydrocarbon group having 1 to 10 carbon atoms in each of R 1 and R 3 include a chain aliphatic group having an ether bond and a cyclic aliphatic group.
  • a furfuryl group is preferred.
  • at least one of R 1 and R 3 is preferably an alkyl group, particularly an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group from the viewpoint of viscosity characteristics.
  • both R 1 and R 3 are alkyl groups, particularly methyl groups.
  • R 2 in the general formula (I) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • the oxyalkylene groups in one molecule may be the same or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferred, and in particular, oxyalkylene units. Those containing 50 mol% or more of oxypropylene units are preferred.
  • n is an integer of 1 to 6, and is determined according to the number of R 1 binding sites.
  • n is 1, and when R 1 is an aliphatic hydrocarbon group having 2, 3, 4, 5 and 6 bonding sites, n Are 2, 3, 4, 5 and 6, respectively.
  • m is a number with an average value of m ⁇ n of 6 to 80, and when the average value exceeds 80, the average value of m ⁇ n is within the above range, for example, the compatibility decreases and the oil return property deteriorates. If deviating from the above, the object of the present invention may not be sufficiently achieved.
  • the polyoxyalkylene glycol represented by the general formula (I) includes a polyoxyalkylene glycol having a hydroxyl group at the terminal, and the content of the hydroxyl group is 50 mol% or less with respect to all terminal groups. If it is the ratio which becomes, even if it contains, it can be used conveniently. If the hydroxyl group content exceeds 50 mol%, the hygroscopicity increases and the viscosity index decreases, which is not preferable. When used in combination with an unsaturated fluorinated hydrocarbon refrigerant described later, the refrigerant has an olefin structure and is therefore less stable, so the base oil preferably has a hydroxyl value of 5 mgKOH / g or less.
  • polyoxyalkylene glycols include those represented by the general formula (Ia)
  • polyoxypropylene glycol monobutyl ether represented by the formula (1) and polyoxypropylene glycol diacetate are preferred.
  • polyoxyalkylene glycols represented by the general formula (I) any of those described in detail in JP-A-2-305893 can be used. In this invention, these polyoxyalkylene glycols may be used individually by 1 type, and may be used in combination of 2 or more type.
  • an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide was polymerized using water or alkali hydroxide as an initiator to obtain a polyoxyalkylene glycol having hydroxyl groups at both ends. Thereafter, both ends of this hydroxyl group can be obtained by etherification or esterification using alkyl halide or acyl halide.
  • a monohydric alcohol having 1 to 10 carbon atoms or an alkali metal salt thereof is used as an initiator, and an alkylene oxide having 2 to 4 carbon atoms is polymerized to have an ether bond at one end and a hydroxyl group at the other end.
  • n 2 or more in the general formula (I)
  • a bivalent to hexavalent polyhydric alcohol may be used as an initiator instead of a monovalent alcohol.
  • the amount of alkyl halide or acyl halide is such that the ratio of polyoxyalkylene glycol or the like to alkyl halide or acyl halide in the etherification or esterification reaction is
  • the amount is less than the stoichiometric amount, the hydroxyl group remains and the hydroxyl value increases. Therefore, it is desirable to optimize the molar ratio of polyoxyalkylene glycol or the like to alkyl halide or acyl halide.
  • coloring can be suppressed by performing superposition
  • polyvinyl ethers that can be used as the base oil in the lubricating oil composition for compression refrigerators of the present invention include those represented by the general formula (II)
  • the main component is a polyvinyl compound having a structural unit represented by: R 4 , R 5 and R 6 in the general formula (II) each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different from each other.
  • the hydrocarbon group is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups.
  • R 4 , R 5 and R 6 are particularly preferably a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms.
  • R 7 in the general formula (II) represents a divalent hydrocarbon group having 2 to 10 carbon atoms.
  • the divalent hydrocarbon group having 2 to 10 carbon atoms specifically refers to Ethylene group, phenylethylene group, 1,2-propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylenes Groups, divalent aliphatic groups such as various nonylene groups and various decylene groups; alicyclic groups having two bonding sites on cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, propylcyclohexane, etc.
  • Divalent aromatic hydrocarbons such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylenes, etc.
  • Elementary group Alkyl group of alkyl aromatic hydrocarbon such as toluene and ethylbenzene and alkyl aromatic group each having a monovalent bonding site on the aromatic part; Alkyl group part of polyalkyl aromatic hydrocarbon such as xylene and diethylbenzene And alkyl aromatic groups having a binding site.
  • aliphatic groups having 2 to 4 carbon atoms are particularly preferred.
  • a plurality of R 7 Os may be the same or different.
  • p represents the number of repetitions, and the average value is an integer in the range of 0 to 10, preferably 0 to 5.
  • R 8 in the general formula (II) represents a hydrocarbon group having 1 to 10 carbon atoms, which is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n Alkyl groups such as -butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups; cyclopentyl group, cyclohexyl group , Various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various propyl cyclohexyl groups, various dimethyl cyclohexyl groups and other cycloalkyl groups; phenyl groups, various methyl phenyl groups, various ethyl phenyl groups, various dimethyl phenyl groups
  • the polyvinyl ether compound of the present invention can be produced by polymerization of a corresponding vinyl ether monomer.
  • Vinyl ether monomers that can be used here are represented by the general formula (III)
  • vinyl ether monomers include various compounds corresponding to the polyvinyl ether compounds, such as vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n butyl ether, Vinyl-isobutyl ether, vinyl-sec-butyl ether, vinyl-tert-butyl ether, vinyl-n-pentyl ether, vinyl-n-hexyl ether, vinyl-2-methoxyethyl ether, vinyl-2-ethoxyethyl ether, vinyl-2 -Methoxy-1-methyl ethyl ether, vinyl-2-methoxy-propyl ether, vinyl-3,6-dioxaheptyl ether, vinyl-3,6,9-trioxadecyl ether, vinyl-1,4-d
  • the polyvinyl ether compound having the structural unit represented by the general formula (II) used as a main component in the lubricating oil composition for a compression type refrigerator of the present invention has a method for indicating a terminal end thereof in the present disclosure and a known method. By this method, it can be converted into a desired structure. Examples of the group to be converted include saturated hydrocarbon groups, ether groups, alcohol groups, ketone groups, amide groups, and nitrile groups.
  • the polyvinyl ether compound used for the base oil in the lubricating oil composition for a compression type refrigerator of the present invention those having the following terminal structure are suitable. That is, (1) One terminal is represented by the general formula (IV)
  • R 9 , R 10 and R 11 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different from each other, and R 12 has 2 carbon atoms
  • divalent hydrocarbon group having to 10 R 13 is a hydrocarbon group having 1 to 10 carbon atoms, q is an average value thereof is an integer of 0 to 10, a plurality of R 12 in the case of R 12 O is more O may be the same or different.
  • V the remaining ends are represented by the general formula (V)
  • R 14 , R 15 and R 16 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different from each other, and R 17 has 2 carbon atoms
  • R 18 is a hydrocarbon group having 1 to 10 carbon atoms
  • r is an average value thereof is an integer of 0 to 10
  • a plurality if R 17 O is more R 17 O may be the same or different.
  • R 19, R 20 and R 21 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the being the same or different
  • R 22 and R 24 Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different from each other
  • R 23 and R 25 each represents a hydrocarbon group having 1 to 10 carbon atoms
  • s and t each represent an integer having an average value of 0 to 10, which may be the same or different from each other
  • a plurality of R 22 O it is more R 22 O may be independently identical or different when there are a plurality of R 24 in the case where there are multiple R 24 O May be the same or different.
  • each of R 26 , R 27 and R 28 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different from each other.
  • It has a structure represented by
  • the polyvinyl ether-based mixture may be a mixture of two or more selected from those having the terminal structures (1) to (4). Preferred examples of such a mixture include a mixture of the above (1) and (4), and a mixture of (2) and (3).
  • the base oil preferably has a hydroxyl value of 17 mgKOH / g or less. 15 mgKOH / g or less is more preferable, and 10 mgKOH / g or less is particularly preferable.
  • the polyvinyl ether compound it is preferable to select the raw materials, the initiator and the reaction conditions so as to produce a polyvinyl ether compound having a preferable viscosity range.
  • this polyvinyl ether type compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Poly (oxy) alkylene glycol refers to both polyalkylene glycol and polyoxyalkylene glycol.
  • poly (oxy) alkylene glycol that can be used as a base oil or a copolymer of its monoether and polyvinyl ether includes general formula (VIII) and general formula (IX)
  • a hydrocarbon group of the general formula R 29 in (VIII), R 30 and R 31 are each a hydrogen atom or a C 1-8, they may be the same or different from each other, R 33 is 2 carbon atoms 4 divalent hydrocarbon group, R 34 is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group optionally having a substituent having 1 to 20 carbon atoms, 2 to 20 acyl groups or oxygen-containing hydrocarbon groups having 2 to 50 carbon atoms, R 32 represents a hydrocarbon group having 1 to 10 carbon atoms, and R 34 , R 33 and R 32 are the same when there are a plurality of them.
  • the hydrocarbon group having 1 to 8 carbon atoms of R 29 to R 31 is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Alkyl group such as butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups; cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, various An aryl group such as a dimethylphenyl group; an arylalkyl group such as a benzyl group, various phenylethyl groups, and various methylbenzyl groups.
  • R ⁇ 29> R ⁇ 30> and R ⁇
  • divalent hydrocarbon group having 2 to 4 carbon atoms represented by R 33 include divalent alkylene groups such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and various butylene groups.
  • v represents the number of repeating R 33 O, and the average value thereof is in the range of 1 to 50, preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5. It is an integer.
  • R 33 O is plural, plural R 33 O may be the same or different.
  • K represents an integer of 1 to 50, preferably 1 to 10, more preferably 1 to 2, particularly preferably 1
  • u represents an integer of 0 to 50, preferably 2 to 25, more preferably 5 to 15.
  • the copolymer may have a block structure or a random structure.
  • R 34 in the general formula (VIII) preferably represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms.
  • Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and various pentyl groups.
  • acyl group having 2 to 10 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, piperoyl group, benzoyl group, and toluoyl group.
  • oxygen-containing hydrocarbon group having 2 to 50 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, 1,1-bismethoxypropyl group, 1,2-bismethoxypropyl group, ethoxy
  • Preferable examples include propyl group, (2-methoxyethoxy) propyl group, (1-methyl-2-methoxy) propyl group and the like.
  • the hydrocarbon group having 1 to 10 carbon atoms represented by R 32 is specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.
  • Alkyl groups such as various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups; cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, Cycloalkyl groups such as various dimethylcyclohexyl groups; aryl groups such as phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups Benzyl group, various phenylethyl groups, various groups An arylalkyl group such as tilbenzyl group, various phenylpropyl groups, various phenylbutyl groups, and
  • the polyvinyl ether copolymer I having the structural unit represented by the general formula (VIII) improves the lubricity, insulation, hygroscopicity and the like while satisfying the compatibility by using the copolymer. There is an effect that can. At this time, by selecting the kind of raw material monomer, the kind of initiator, and the ratio of the copolymer, the performance of the oil can be adjusted to the target level. Therefore, there is an effect that an oil agent can be freely obtained in accordance with requirements such as lubricity and compatibility that differ depending on the type of compressor, the material of the lubrication part, the refrigerating capacity, the type of refrigerant, and the like in the refrigeration system or the air conditioning system.
  • R 29 to R 32 , R 33 and v are the same as described above.
  • R 33 and R 32 may be the same or different when there are a plurality of them.
  • x and y each represents an integer of 1 to 50, and when x and y are plural, the copolymer may be a block structure or a random structure.
  • X and Y each independently represent a hydrogen atom, a hydroxyl group or 1 to 20 hydrocarbon groups.
  • the method for producing the polyvinyl ether copolymer I represented by the general formula (VIII) is not particularly limited as long as it is a method by which it can be obtained.
  • the production methods 1 to 3 shown below are used. Can be manufactured.
  • (Production method 1 of polyvinyl ether copolymer I) In this production method 1, the general formula (X) R 34 — (OR 33 ) v —OH (X) (Wherein R 33 , R 34 and v are the same as above).
  • a polyvinyl ether copolymer I By polymerizing a vinyl ether compound represented by the following formula, a polyvinyl ether copolymer I can be obtained.
  • the poly (oxy) alkylene glycol compound represented by the general formula (X) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol.
  • (oxy) alkylene glycol monoethers such as monomethyl ether.
  • Examples of the vinyl ether compound represented by the general formula (XI) include vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n butyl ether, vinyl isobutyl ether, Vinyl ethers such as vinyl-sec-butyl ether, vinyl-tert-butyl ether, vinyl-n-pentyl ether, vinyl-n-hexyl ether; 1-methoxypropene, 1-ethoxypropene, 1-n-propoxypropene, 1-iso Propoxypropene, 1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene, 1-tert-butoxypropene, 2-methoxypropene, 2-ethoxypropene, 2-n-propoxypropene, 2- Propenes such as sopropoxypropene, 2-n-butoxypropene, 2-isobutoxypropene, 2-sec-butoxypropene
  • a polyvinyl ether copolymer I can be obtained by polymerizing the vinyl ether compound represented by the general formula (XI) using the acetal compound represented by formula (II) as an initiator.
  • the acetal compound represented by the general formula (XII) include acetaldehyde methyl (2-methoxyethyl) acetal, acetaldehyde ethyl (2-methoxyethyl) acetal, acetaldehyde methyl (2-methoxy 1-methylethyl) acetal, and acetaldehyde.
  • the acetal compound represented by the general formula (XII) includes, for example, one molecule of a poly (oxy) alkylene glycol compound represented by the general formula (X) and a vinyl ether type represented by the general formula (XI). It can also be produced by reacting one molecule of the compound. The obtained acetal compound can be isolated or used as it is as an initiator.
  • the vinyl ether copolymer I can be obtained by polymerizing the vinyl ether compound represented by the general formula (XI) using the acetal compound represented by formula (II) as an initiator.
  • Examples of the acetal compound represented by the general formula (XIII) include acetaldehyde di (2-methoxyethyl) acetal, acetaldehyde di (2-methoxy-1-methylethyl) acetal, acetaldehyde di [2- (2-methoxyethoxy ) Ethyl] acetal, acetaldehyde di [2- (2-methoxyethoxy) -1-methylethyl] acetal, and the like.
  • the acetal compound represented by the general formula (XIII) includes, for example, one molecule of a poly (oxy) alkylene glycol compound represented by the general formula (X) and the general formula (XIV).
  • R 29 to R 31 , R 33 , R 34 and v are the same as described above.
  • It can also be produced by reacting with one molecule of a vinyl ether compound represented by the formula:
  • the obtained acetal compound can be isolated or used as it is as an initiator.
  • One end of the vinyl ether copolymer I represented by the general formula (VIII) is represented by the general formula (XV) or (XVI).
  • R 29 to R 34 and v are the same as above). It can be set as the polyvinyl ether type copolymer I which has a structure represented by these.
  • polyvinyl ether copolymers I the following are particularly suitable as the base oil for the lubricating oil composition for a compression type refrigerator of the present invention.
  • One terminal is represented by the general formula (XV) or (XVI), and the remaining terminal is a structure represented by the general formula (XVII) or (XVIII).
  • R 29 , R 30 and R 31 are both hydrogen atoms, v is an integer of 1 to 4, R 33 is a divalent hydrocarbon group having 2 to 4 carbon atoms, R 34 is an alkyl group having 1 to 10 carbon atoms, and R 32 is a hydrocarbon group having 1 to 10 carbon atoms.
  • One terminal is represented by the general formula (XV) and the other terminal is represented by the general formula (XVIII), and R 29 , R 30 and R 31 in the general formula (VIII) Are both hydrogen atoms, v is an integer of 1 to 4, R 33 is a divalent hydrocarbon group having 2 to 4 carbon atoms, R 34 is an alkyl group having 1 to 10 carbon atoms, and R 32 is an alkyl group having 1 to 10 carbon atoms. A hydrocarbon group.
  • One terminal is represented by the general formula (XVI) and the other terminal is represented by the general formula (XVII), and R 29 , R 30 and R 31 in the general formula (VIII) are both hydrogen atoms, v is an integer of 1 to 4, R 33 is a divalent hydrocarbon group having 2 to 4 carbon atoms, R 34 is an alkyl group having 1 to 10 carbon atoms, and R 32 is an alkyl group having 1 to 10 carbon atoms. A hydrocarbon group.
  • the method for producing the polyvinyl ether copolymer II represented by the general formula (IX) is not particularly limited as long as it is a method by which it can be obtained, but it is efficiently produced by the method described below. can do.
  • the polyvinyl ether copolymer II represented by the general formula (IX) is represented by the general formula (XIX) HO- (R 33 O) v -H (XIX) (Wherein R 33 and v are the same as described above.) It can obtain by polymerizing the vinyl ether compound represented by the said general formula (XI), using poly (oxy) alkylene glycol represented by these as an initiator.
  • poly (oxy) alkylene glycol represented by the general formula (XIX) examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol.
  • the refrigerant When used in combination with an unsaturated fluorinated hydrocarbon refrigerant described later, the refrigerant has an olefin structure and is therefore poor in stability, so the base oil preferably has a hydroxyl value of 15 mgKOH / g or less.
  • this poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether may be used singly or in combination of two or more.
  • the polyol ester that can be used as the base oil in the lubricating oil composition for a compression refrigerator of the present invention includes a diol or a polyol having about 3 to 20 hydroxyl groups and a fatty acid having about 1 to 24 carbon atoms. Esters are preferably used.
  • diol examples include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5- Pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. Can be mentioned.
  • polyol examples include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), and tri- (pentaerythritol).
  • Glycerin polyglycerin (glycerin 2-20 mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol; xylose, arabinose , Ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose Gentianose, saccharides such as Merenjitosu; and their partially etherified products and methyl glucosides (glycosides) and the like.
  • polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol; xylose, arabinose , Ribose
  • polyols include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri Hindered alcohols such as-(pentaerythritol) are preferred.
  • the number of carbon atoms is not particularly limited, but those having 1 to 24 carbon atoms are usually used.
  • those having 3 or more carbon atoms are preferable, those having 4 or more carbon atoms are more preferable, those having 5 or more carbon atoms are more preferable, and those having 10 or more carbon atoms are more preferable.
  • the above is most preferable.
  • a C18 or less thing is preferable, a C12 or less thing is more preferable, and a C9 or less thing is still more preferable.
  • any of a linear fatty acid and a branched fatty acid may be sufficient, a linear fatty acid is preferable from the point of lubricity, and a branched fatty acid is preferable from the point of hydrolysis stability. Furthermore, either saturated fatty acid or unsaturated fatty acid may be used.
  • fatty acid examples include, for example, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid.
  • linear or branched acids such as acid, nonadecanoic acid, icosanoic acid and oleic acid; More specifically, valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid) Capric acid (n-decanoic acid), oleic acid (cis-9-octadecenoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3, 5,5-trimethylhexanoic acid and the like are preferable.
  • valeric acid n-pentanoic acid
  • caproic acid n-hexanoic acid
  • enanthic acid n-heptanoi
  • the polyol ester may be a partial ester remaining without all the hydroxyl groups of the polyol being esterified, or may be a complete ester in which all the hydroxyl groups are esterified, or a partial ester and a complete ester. A complete ester is preferable.
  • neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythris More preferred are esters of hindered alcohols such as lithol, di- (pentaerythritol), tri- (pentaerythritol), and further esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol.
  • the ester of pentaerythritol is the most preferable because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.
  • preferred polyol esters include neopentyl glycol, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, Diester of one or more fatty acids selected from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; trimethylolethane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid
  • the ester with two or more fatty acids may be a mixture of two or more esters of one type of fatty acid and polyol.
  • the refrigerant When used in combination with an unsaturated fluorinated hydrocarbon refrigerant described later, the refrigerant has an olefin structure and is therefore less stable. Therefore, the base oil has an acid value of 0.02 mgKOH / g or less and a hydroxyl value. Is preferably 5 mgKOH / g or less.
  • the acid value is more preferably 0.01 mgKOH / g or less, and the hydroxyl value is more preferably 3 mgKOH / g or less.
  • the base oil has an ASTM color of 1 or less, an interfacial tension of 20 mN / m or more, an extraction water pH of 5.5 or more, an ash content of 0.1% by mass or less, and a volume resistance of 10 9 ⁇ m or more. It is preferable.
  • a base oil having such properties is preferable because of its good stability and excellent electrical insulation.
  • coloring can be suppressed by performing an esterification reaction in an inert gas atmosphere.
  • the amount of the aliphatic monocarboxylic acid is less than the stoichiometric amount in the ratio of the polyhydric alcohol to be reacted and the aliphatic monocarboxylic acid, the hydroxyl group remains and the hydroxyl value increases.
  • the amount is larger than the stoichiometric amount, the carboxylic acid remains, the acid value increases, and the pH of the extracted water decreases. Therefore, it is desirable to optimize the molar ratio of the polyhydric alcohol to the aliphatic monocarboxylic acid, and it is desirable to carry out a treatment to reduce the amount of the remaining esterification catalyst (ash content) as much as possible.
  • polycarbonates that can be used as the base oil in the lubricating oil composition for compression refrigerators of the present invention include polycarbonates having two or more carbonate bonds in one molecule, that is, the general formula (XX)
  • Z is a residue obtained by removing a hydroxyl group from an e-valent alcohol having 1 to 12 carbon atoms
  • R 35 is a linear or branched alkylene group having 2 to 10 carbon atoms
  • R 36 is 1 to 12 carbon atoms.
  • Monovalent hydrocarbon group or R 38 (O—R 37 ) f — (where R 38 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 37 is a straight chain having 2 to 10 carbon atoms.
  • a chain or branched alkylene group, f represents an integer of 1 to 20, and a group containing an ether bond, c is an integer of 1 to 30, d is an integer of 1 to 50, and e is an integer of 1 to 6. Is shown.)
  • R 39 is a linear or branched alkylene group having 2 to 10 carbon atoms, g is an integer of 1 to 20, and Z, R 35 , R 36 , c, d and e are the same as above. is there.)
  • Preferable examples include at least one selected from the compounds represented by:
  • Z is a residue obtained by removing a hydroxyl group from a monovalent to hexavalent alcohol having 1 to 12 carbon atoms. A residue obtained by removing a hydroxyl group from the alcohol is preferable.
  • Examples of monovalent to hexavalent alcohols having 1 to 12 carbon atoms having Z as a residue include monovalent alcohols such as methyl alcohol, ethyl alcohol, n- or isopropyl alcohol, various butyl alcohols, various pentyl alcohols, various Aliphatic monohydric alcohols such as hexyl alcohol, various octyl alcohols, various decyl alcohols and various dodecyl alcohols; alicyclic monohydric alcohols such as cyclopentyl alcohol and cyclohexyl alcohol; aromatic alcohols such as phenol, cresol, xylenol, butylphenol and naphthol Araliphatic alcohols such as benzyl alcohol and phenethyl alcohol are used as divalent alcohols such as ethylene glycol, propylene glycol, butylene glycol, neope Aliphatic alcohols such as tylene glycol and tetramethylene glycol; cycloaliphatic alcohols
  • the residue obtained by removing the hydroxyl group from the monovalent alcohol having 1 to 12 carbon atoms represented by R 40 includes a methyl group, an ethyl group, n -Aliphatic hydrocarbon groups such as propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups; cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl Group, alicyclic hydrocarbon group such as decahydronaphthyl group; aromatic hydrocarbon group such as phenyl group, various tolyl groups, various xy
  • R 35 is a linear or branched alkylene group having 2 to 10 carbon atoms. Among them, those having 2 to 6 carbon atoms are preferable, and ethylene and propylene groups are particularly preferable from the viewpoint of performance and ease of production. Is preferred.
  • R 36 is a monovalent hydrocarbon group having 1 to 12 carbon atoms or R 38 (O—R 37 ) f — (wherein R 38 is a hydrogen atom or one having 1 to 12, preferably 1 to 6 carbon atoms).
  • R 37 is a group having an ether bond represented by the following formula: R 37 is a linear or branched alkylene group having 2 to 10 carbon atoms, and f is an integer of 1 to 20.
  • Examples of ⁇ 12 monovalent hydrocarbon groups are the same as those exemplified in the description of R 40 .
  • R 36 is particularly preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
  • the linear or branched alkylene group having 2 to 10 carbon atoms represented by R 39 includes those having 2 to 6 carbon atoms for the same reason as in the case of R 35.
  • An ethylene group and a propylene group are particularly preferable.
  • Such a polycarbonate compound can be produced by various methods. Usually, a carbonate ester-forming derivative such as a carbonic acid diester or phosgene is reacted with an alkylene glycol or a polyoxyalkylene glycol according to a known method. The polycarbonate compound can be produced. In this invention, these polycarbonates may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the base oil in the lubricating oil composition for a compression type refrigerator of the present invention, the aforementioned polyoxyalkylene glycols, polyvinyl ethers, poly (oxy) alkylene glycols or copolymers of monoethers thereof and polyvinyl ethers, Those containing at least one oxygen-containing compound selected from polyol esters and polycarbonates as a main component are preferably used.
  • containing as a main component means containing the said oxygen-containing compound in the ratio of 50 mass% or more.
  • the content of the oxygen-containing compound in the base oil is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.
  • the base oil has a kinematic viscosity at 100 ° C. of preferably 1 mm 2 / s to 50 mm 2 / s, more preferably 3 mm 2 / s to 40 mm 2 / s, and even more preferably 4 mm 2 / s. s to 30 mm 2 / s. If the kinematic viscosity is 1 mm 2 / s or more, good lubrication performance (load resistance) is exhibited, and the sealing property is good, and if it is 50 mm 2 / s or less, the energy saving property is also good. is there.
  • the number average molecular weight of the base oil is preferably 300 or more and 3000 or less, more preferably 500 or more and 3000 or less, and further preferably 700 or more and 2500 or less.
  • the flash point of the base oil is preferably 150 ° C. or higher. However, if the number average molecular weight of the base oil is 300 or more and 3000 or less, desired performance as a refrigerating machine oil can be exhibited, and the base oil is flammable. A point can be within the range.
  • the viscosity index of the base oil in the present invention is preferably 60 or more, and more preferably 80 or more.
  • the upper limit of the viscosity index is about 300 due to manufacturing restrictions.
  • the viscosity index of the base oil is measured in accordance with JIS K 2283.
  • the base oil has the above-mentioned properties, it is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, together with the oxygen-containing compound.
  • Those containing a base oil can be used, but those containing no other base oil are more preferred.
  • Examples of the base oil that can be used in combination with the oxygen compound include other polyesters, hydrides of ⁇ -olefin oligomers, mineral oil, alicyclic hydrocarbon compounds, alkylated aromatic hydrocarbon compounds, and the like.
  • a refrigerant containing a saturated fluorinated hydrocarbon compound (HFC) having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms is used.
  • saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms examples include trifluoromethane, difluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1 , 1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 1,1,1,3,3-pentafluoropropane Is preferred.
  • These refrigerants may be used alone or in combination of two or more.
  • R32 difluoromethane
  • R32 is preferably used alone, but R32 is mixed with 1,1,1,2,2-pentafluoroethane (R125).
  • R32, R125, and 1,1,1,2-tetrafluoroethane (R134a) may be mixed.
  • a typical example of the former is R410A, and a typical example of the latter is R407C.
  • the ratio of R32 in the whole refrigerant is preferably 20% by mass or more, and 40% by mass or more Is more preferable, and 70% by mass or more is more preferable.
  • the saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms may be mixed with a refrigerant other than the saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms.
  • the mixing ratio of the refrigerant other than the saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms is preferably 30% by mass or less, more preferably 20% by mass or less based on the whole refrigerant.
  • the refrigerant other than the saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms is selected from carbon dioxide (CO 2 ), low boiling point hydrocarbon (HC), ammonia, or a compound represented by the following molecular formula (A). There may be mentioned at least one fluorine-containing organic compound.
  • the molecular formula (A) represents the type and number of elements in the molecule, and the formula (A) represents a fluorine-containing organic compound having 1 to 6 carbon atoms C.
  • a fluorine-containing organic compound having 1 to 6 carbon atoms can have physical and chemical properties such as boiling point, freezing point, and latent heat of vaporization required as a refrigerant.
  • the bond form of p carbon atoms represented by C p includes carbon-carbon single bond, unsaturated bond such as carbon-carbon double bond, carbon-oxygen double bond, etc. It is.
  • the carbon-carbon unsaturated bond is preferably a carbon-carbon double bond from the viewpoint of stability, and the number thereof is 1 or more, but 1 is preferable.
  • the bonding form of q oxygen atoms represented by O q is preferably oxygen derived from an ether group, a hydroxyl group or a carbonyl group.
  • the number q of oxygen atoms may be 2 and includes the case of having two ether groups, hydroxyl groups and the like.
  • p is 2 to 6, and the molecule has one or more unsaturated bonds such as a carbon-carbon double bond.
  • R represents Cl, Br, I, or H, and any of these may be used. However, since R is less likely to destroy the ozone layer, R may be H. preferable.
  • preferable examples of the fluorine-containing organic compound represented by the molecular formula (A) include unsaturated fluorinated hydrocarbon compounds, fluorinated ether compounds, fluorinated alcohol compounds, and fluorinated ketone compounds. Hereinafter, these compounds will be described.
  • the unsaturated fluorinated hydrocarbon compound used as the refrigerant of the refrigerator is, for example, in the molecular formula (A), R is H, p is 2 to 6, q is 0, and r is 1 to 12 , S is an unsaturated fluorinated hydrocarbon compound in which each integer is from 0 to 11.
  • unsaturated fluorinated hydrocarbon compounds include fluorinated products of linear or branched chain olefins having 2 to 6 carbon atoms and cyclic olefins having 4 to 6 carbon atoms.
  • ethylene having 1 to 3 fluorine atoms introduced propene having 1 to 5 fluorine atoms introduced, butenes having 1 to 7 fluorine atoms introduced, 1 to 9 Pentenes introduced with fluorine atoms, hexenes introduced with 1 to 11 fluorine atoms, cyclobutene introduced with 1 to 5 fluorine atoms, cyclopentene introduced with 1 to 7 fluorine atoms, 1 And cyclohexene introduced with up to 9 fluorine atoms.
  • unsaturated fluorinated hydrocarbon compounds having 2 to 3 carbon atoms are preferred, and examples thereof include ethylene fluorides such as trifluoroethylene and various propene fluorides.
  • the fluoride is more preferable.
  • propene fluoride include 3,3,3-trifluoropropene, 1,3,3,3-tetrafluoropropene, and 2,3,3,3-tetrafluoropropene.
  • 1,2,3,3,3-pentafluoropropene HFO1225ye
  • 1,3,3,3-tetrafluoropropene HFO1234ze
  • 2,3,3,3-tetrafluoropropene HFO1234yf
  • this unsaturated fluorinated hydrocarbon compound may be used alone or in combination of two or more.
  • a fluorinated ether compound is preferably a fluorinated product of, for example, a chain aliphatic ether having 2 to 6 carbon atoms, having 1 to 2 ether bonds, and an alkyl group being linear or branched.
  • fluorinated cyclic aliphatic ethers having 3 to 6 carbon atoms and having 1 to 2 ether bonds.
  • fluorinated dimethyl ether introduced with 1 to 6 fluorine atoms fluorinated methyl ethyl ether introduced with 1 to 8 fluorine atoms, and fluorinated with 1 to 8 fluorine atoms introduced Dimethoxymethane, fluorinated methyl propyl ethers with 1 to 10 fluorine atoms introduced, 1 fluorinated methyl butyl ethers with 1 to 12 fluorine atoms introduced, 1 to 12 fluorine atoms with a fluorine atom introduced Ethyl propyl ethers, oxetane fluoride with 1-6 fluorine atoms introduced, 1,3-dioxolane fluoride with 1-6 fluorine atoms introduced, 1-8 fluorine atoms introduced And fluorinated tetrahydrofuran.
  • fluorinated ether compounds include hexafluorodimethyl ether, pentafluorodimethyl ether, bis (difluoromethyl) ether, fluoromethyl trifluoromethyl ether, trifluoromethyl methyl ether, perfluorodimethoxymethane, 1-trifluoromethoxy-1, 1,2,2-tetrafluoroethane, difluoromethoxypentafluoroethane, 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane, 1-difluoromethoxy-1,1,2,2-tetrafluoroethane 1-difluoromethoxy-1,2,2,2-tetrafluoroethane, 1-trifluoromethoxy-2,2,2-trifluoroethane, 1-difluoromethoxy-2,2,2-trifluoroethane, perfluoro Kisetan, perfluoro-1,3-dioxolane, various isomers of pentafluoro
  • examples of the fluorinated alcohol compound used as the refrigerant of the refrigerator include, for example, in the molecular formula (A), R is H, p is 1 to 6, q is 1 to 2, r is 1 to 13, Examples include fluorinated ether compounds in which s is an integer of 1 to 13.
  • Preferable examples of such a fluorinated alcohol compound include a fluorinated product of a linear or branched aliphatic alcohol having 1 to 6 carbon atoms and having 1 to 2 hydroxyl groups.
  • fluorinated methyl alcohol with 1 to 3 fluorine atoms introduced fluorinated ethyl alcohol with 1 to 5 fluorine atoms introduced, and fluorinated with 1 to 7 fluorine atoms introduced
  • fluorinated butyl alcohols having 1 to 9 fluorine atoms introduced fluorinated pentyl alcohols having 1 to 11 fluorine atoms introduced, and fluorines having 1 to 4 fluorine atoms introduced
  • fluorinated alcohol compounds include monofluoromethyl alcohol, difluoromethyl alcohol, trifluoromethyl alcohol, various isomers of difluoroethyl alcohol, various isomers of trifluoroethyl alcohol, various isomers of tetrafluoroethyl alcohol, Various isomers of pentafluoroethyl alcohol and difluoropropyl alcohol, various isomers of trifluoropropyl alcohol, various isomers of tetrafluoropropyl alcohol, various isomers of pentafluoropropyl alcohol, various isomers of hexafluoropropyl alcohol, hepta Fluoropropyl alcohol, difluorobutyl alcohol isomers, trifluorobutyl alcohol isomers, tetrafluorobutyl alcohol Fluorinated alcohols such as isomers, various isomers of pentafluorobutyl alcohol, various isomers of hexafluoro
  • fluorinated ketone compounds examples of the fluorinated ketone compound used as the refrigerant of the refrigerator include, for example, in the molecular formula (A), R is H, p is 2 to 6, q is 1 to 2, r is 1 to 12, Examples thereof include fluorinated ketone compounds in which s is an integer of 0 to 11.
  • fluorinated ketone compound include fluorinated products of aliphatic ketones having 3 to 6 carbon atoms and linear or branched alkyl groups.
  • fluorinated acetone introduced with 1 to 6 fluorine atoms
  • fluorinated methyl ethyl ketone introduced with 1 to 8 fluorine atoms
  • fluorinated diethyl ketone introduced with 1 to 10 fluorine atoms
  • fluorinated methyl propyl ketones having 1 to 10 fluorine atoms introduced therein.
  • fluorinated ketone compounds examples include hexafluorodimethyl ketone, pentafluorodimethyl ketone, bis (difluoromethyl) ketone, fluoromethyl trifluoromethyl ketone, trifluoromethyl methyl ketone, perfluoromethyl ethyl ketone, and trifluoromethyl-1,1.
  • 2,2-tetrafluoroethyl ketone difluoromethyl pentafluoroethyl ketone, trifluoromethyl-1,1,2,2-tetrafluoroethyl ketone, difluoromethyl-1,1,2,2-tetrafluoroethyl ketone, Examples thereof include difluoromethyl-1,2,2,2-tetrafluoroethyl ketone, trifluoromethyl-2,2,2-trifluoroethyl ketone, and difluoromethyl-2,2,2-trifluoroethyl ketone.
  • these fluorinated ketone compounds may be used alone or in combination of two or more.
  • the refrigerator oil composition of the present invention contains at least one additive selected from among extreme pressure agents, oiliness agents, antioxidants, acid scavengers, metal deactivators and antifoaming agents. Can do. (Extreme pressure agent)
  • the extreme pressure agent include phosphorus extreme pressure agents such as phosphate esters, acid phosphate esters, phosphite esters, acid phosphite esters, and amine salts thereof.
  • tricresyl phosphate trithiophenyl phosphate, tri (nonylphenyl) phosphite, dioleyl hydrogen phosphite, 2-ethylhexyl diphenyl phosphite in terms of extreme pressure and friction characteristics Etc. are particularly preferred.
  • the metal salt of carboxylic acid is mentioned.
  • the metal salt of a carboxylic acid here is preferably a carboxylic acid having 3 to 60 carbon atoms, more preferably a metal salt of a fatty acid having 3 to 30 carbon atoms, particularly preferably 12 to 30 carbon atoms.
  • dimer acid and trimer acid of the fatty acid and metal salt of dicarboxylic acid having 3 to 30 carbon atoms can be mentioned.
  • metal salts of fatty acids having 12 to 30 carbon atoms and dicarboxylic acids having 3 to 30 carbon atoms are particularly preferred.
  • an alkali metal or an alkaline earth metal is preferable, and an alkali metal is particularly optimal.
  • extreme pressure agents as extreme pressure agents other than those described above, for example, sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates, thioterpenes, dialkylthiodipropionates, etc.
  • the sulfur type extreme pressure agent can be mentioned.
  • the blending amount of the extreme pressure agent is preferably 0.001 to 5% by mass and more preferably 0.005 to 3% by mass based on the total amount of the composition from the viewpoint of lubricity and stability.
  • One of these extreme pressure agents may be used alone, or two or more thereof may be used in combination.
  • oily agents examples include aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid, polymerized fatty acids such as dimer acid and hydrogenated dimer acid, hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid, lauryl Aliphatic saturated and unsaturated monoalcohols such as alcohol, oleyl alcohol, aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine, aliphatic saturated and unsaturated monocarboxylic amides such as lauric acid amide, oleic acid amide, glycerin And partial esters of polyhydric alcohols such as sorbitol and aliphatic saturated or unsaturated monocarboxylic acids. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the blending amount is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on
  • Antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-tert -Butylphenol) and the like, phenyl- ⁇ -naphthylamine, N.I.
  • An amine-based antioxidant such as N′-di-phenyl-p-phenylenediamine is preferably blended. The antioxidant is preferably contained in the composition in an amount of 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, from the viewpoint of effects and economy.
  • the acid scavenger examples include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil. At least one selected from glycidyl ester, glycidyl ether and ⁇ -olefin oxide is preferably used.
  • the glycidyl ester is a linear, branched or cyclic saturated or unsaturated aliphatic or aromatic carboxylic acid having usually 3 to 30, preferably 4 to 24, more preferably 6 to 16 carbon atoms.
  • the aliphatic carboxylic acid or aromatic carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid.
  • it is preferable that all of the carboxyl groups are glycidyl esterified from the viewpoint of suppressing an increase in acid value for the stability of the lubricating oil composition.
  • glycidyl esters of straight-chain, branched and cyclic saturated aliphatic monocarboxylic acids having 6 to 16 carbon atoms are particularly preferred.
  • examples of such glycidyl esters include 2-ethylhexanoic acid glycidyl ester, 3,5,5-trimethylhexanoic acid glycidyl ester, capric acid glycidyl ester, lauric acid glycidyl ester, versatic acid glycidyl ester, and myristic acid glycidyl ester.
  • 2-ethylhexanoic acid glycidyl ester 3,5,5-trimethylhexanoic acid glycidyl ester
  • capric acid glycidyl ester capric acid glycidyl ester
  • lauric acid glycidyl ester lauric acid glycidyl ester
  • versatic acid glycidyl ester and
  • glycidyl ether a linear, branched, cyclic saturated or unsaturated aliphatic mono- or polyhydric alcohol having 3 to 30, preferably 4 to 24, more preferably 6 to 16 carbon atoms, or Examples thereof include glycidyl ether derived from an aromatic compound containing one or more hydroxyl groups. In the case of an aliphatic polyhydric alcohol or an aromatic compound containing two or more hydroxyl groups, all of the hydroxyl groups must be glycidyl etherified from the viewpoint of suppressing an increase in the hydroxyl value for the stability of the lubricating oil composition. preferable.
  • glycidyl ether derived from a linear, branched or cyclic saturated aliphatic monoalcohol having 6 to 16 carbon atoms is particularly preferable.
  • examples of such glycidyl ether include 2-ethylethyl glycidyl ether, isononyl glycidyl ether, caprinoyl glycidyl ether, lauryl glycidyl ether, and myristyl glycidyl ether.
  • the ⁇ -olefin oxide those having generally 4 to 50 carbon atoms, preferably 4 to 24 carbon atoms, more preferably 6 to 16 carbon atoms are used.
  • the acid scavenger may be used alone or in combination of two or more.
  • the blending amount is usually in the range of 0.005 to 10% by mass, particularly 0.05 to 6% by mass, based on the total amount of the composition, from the viewpoint of effect and suppression of sludge generation.
  • Metal deactivator antifoaming agent
  • the metal deactivator include copper deactivators such as N- [N, N′-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl] triazole, and the like.
  • the agent include silicone oil and fluorinated silicone oil.
  • the lubricating oil composition for a compression type refrigerator of the present invention is suitable for a refrigerator using the refrigerant containing the saturated fluorocarbon having 1 to 3 carbon atoms.
  • the amount of the various refrigerants and the lubricating oil composition for the refrigerator is about the mass ratio of the refrigerant / the lubricating oil composition for the refrigerator. It is preferably in the range of 99/1 to 10/90, more preferably 95/5 to 30/70.
  • the lubricating oil composition for a refrigerator according to the present invention can be used in various refrigerators, and is particularly preferably applicable to a compression refrigeration cycle of a compression refrigerator.
  • the refrigerator to which the lubricating oil composition for a refrigerator of the present invention is applied is a compressor, a condenser, an expansion mechanism (an expansion valve or the like) and an evaporator, or a compressor, a condenser, an expansion mechanism, a dryer and an evaporator.
  • the above-described lubricating oil composition for a refrigerator according to the present invention is used as the refrigerator oil, and the above-described various refrigerants are used as the refrigerant.
  • the dryer is preferably filled with a desiccant made of zeolite having a pore diameter of 0.33 nm or less. Examples of the zeolite include natural zeolite and synthetic zeolite.
  • the zeolite has a CO 2 gas absorption capacity of 1% or less at 25 ° C. and a CO 2 gas partial pressure of 33 kPa.
  • Examples of such synthetic zeolite include trade names XH-9 and XH-600 manufactured by Union Showa Co., Ltd.
  • the sliding portion is preferably made of an engineering plastic, or has an organic coating film or an inorganic coating film, particularly in terms of sealing properties.
  • the engineering plastic for example, polyamide resin, polyphenylene sulfide resin, polyacetal resin and the like can be preferably mentioned in terms of sealing properties, slidability, wear resistance, and the like.
  • organic coating film for example, fluorine-containing resin coating film (polytetrafluoroethylene coating film, etc.), polyimide coating film, polyamideimide coating film, And a thermosetting insulating film formed using a resin base material composed of a polyhydroxy ether resin and a polysulfone-based resin and a resin paint containing a crosslinking agent.
  • examples of the inorganic coating film include a graphite film, a diamond-like carbon film, a nickel film, a molybdenum film, a tin film, and a chromium film in terms of sealing properties, slidability, and wear resistance.
  • This inorganic coating film may be formed by a plating process, or may be formed by a PVD method (physical vapor deposition method).
  • a conventional alloy system such as an Fe-based alloy, an Al-based alloy, a Cu-based alloy, or the like can also be used.
  • the lubricating oil composition for a compression refrigerator of the present invention can be used for, for example, a car air conditioner, an electric car air conditioner, a gas heat pump, an air conditioner, a refrigerator, a vending machine, a showcase, various hot water supply systems, a refrigeration / heating system, and the like. it can.
  • 300 mass ppm or less is preferable and, as for the water content in each said system to which the lubricating oil composition for refrigerators is applied, 200 mass ppm or less is more preferable.
  • the residual air partial pressure in the system is preferably 10 kPa or less, and more preferably 5 kPa or less.
  • the lubricating oil composition for a compression type refrigerator of the present invention contains a specific oxygen-containing compound as a main component as a base oil, has a low viscosity, and can improve energy saving. Excellent sealing performance.
  • Base oil / A1 Polyethyl vinyl ether (100 ° C. kinematic viscosity: 15.97 mm 2 / s, flash point: 222 ° C., number average molecular weight: 1250, viscosity index: 85)
  • A2 Polypropylene glycol dimethyl ether (100 ° C.
  • A3 Polypropylene glycol (PPG) / polyethyl vinyl ether (PEV) copolymer (PPG / PEV molar ratio 7/11) (100 ° C.
  • kinematic viscosity 9.56 mm 2 / s, flash point: 218 ° C., number average molecular weight : 1200, viscosity index: 140)
  • A4 pentaerythritol octanoic acid (C8 acid) nonanoic acid (C9 acid) ester (C8 acid / C9 acid molar ratio: 1 / 1.1) (100 ° C.
  • Examples 1 to 9 and Comparative Examples 1 to 7 A lubricating oil composition for a refrigerator having the composition shown in Tables 1 and 2 was prepared, and R32 (difluoromethane) or R410A (mass ratio 50:50 mixture of R32 and R125 (pentafluoroethane)) was used as a refrigerant. Used to evaluate the thermal stability characteristics of the composition. The results are shown in Tables 1 and 2.
  • Comparative Example 1 using the same lubricating oil composition for a compression type refrigerator that does not use a stabilizer in the present invention and using R32 (100% difluoromethane) as the refrigerant is R410A (R32 and R125) as the refrigerant.
  • R32 100% difluoromethane
  • R410A R32 and R125
  • the acid value was higher than that of Comparative Example 2 using a mixed refrigerant (mass ratio of 50:50), and the oil appearance was orange and yellow.
  • the lubricating oil composition for a compression-type refrigerator of the present invention has a low global warming potential, and in particular, a refrigerant using a saturated fluorocarbon having 1 to 3 carbon atoms, which is a refrigerant that can be used for air conditioners, car air conditioners, and the like. It is used for compression type refrigerators that use and exhibits excellent heat and oxidation stability.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une composition d'huile lubrifiante pour un réfrigérateur à compression, dans laquelle au moins un composé organique ayant une double liaison dans la molécule de celui-ci est contenu dans une huile de base, l'au moins un composé organique étant choisi parmi un composé organique ayant au moins deux doubles liaisons non conjuguées dans la molécule, un composé de terpène ayant une double liaison dans la molécule et un hydrocarbure insaturé aliphatique ayant une double liaison dans la molécule et ayant de 12 à 30 atomes de carbone. La composition d'huile lubrifiante présente une excellente stabilité thermique et chimique lorsqu'elle est utilisée dans un réfrigérateur à compression qui utilise un milieu réfrigérant d'hydrocarbure fluoré saturé ayant moins d'atomes de carbone et ayant un potentiel de réchauffement global plus faible.
PCT/JP2011/072162 2010-09-28 2011-09-28 Composition d'huile lubrifiante pour réfrigérateur à compression WO2012043617A1 (fr)

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KR1020137007470A KR101837222B1 (ko) 2010-09-28 2011-09-28 압축형 냉동기용 윤활유 조성물
US13/822,894 US20130274163A1 (en) 2010-09-28 2011-09-28 Lubricant oil composition for compression refrigerator
CN201180043871.6A CN103108944B (zh) 2010-09-28 2011-09-28 压缩型冷冻机用润滑油组合物
EP11829170.7A EP2623583B1 (fr) 2010-09-28 2011-09-28 Composition pour réfrigérateur à compression
US14/931,879 US10774252B2 (en) 2010-09-28 2015-11-04 Lubricant oil composition for compression refrigerator

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JP2010217917A JP5759696B2 (ja) 2010-09-28 2010-09-28 圧縮型冷凍機用潤滑油組成物
JP2010-217917 2010-09-28

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US14/931,879 Division US10774252B2 (en) 2010-09-28 2015-11-04 Lubricant oil composition for compression refrigerator

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WO2016080149A1 (fr) * 2014-11-19 2016-05-26 出光興産株式会社 Composition lubrifiante pour machines frigorifiques et machine frigorifique

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JP2013014673A (ja) * 2011-07-01 2013-01-24 Idemitsu Kosan Co Ltd 圧縮型冷凍機用潤滑油組成物
JP6122861B2 (ja) * 2012-09-28 2017-04-26 出光興産株式会社 圧縮型冷凍機用潤滑油
CN103525370A (zh) * 2013-08-01 2014-01-22 广东美芝制冷设备有限公司 组合物以及采用该组合物的压缩机和制冷设备
JP6456310B2 (ja) 2014-02-05 2019-01-23 Ｊｘｔｇエネルギー株式会社 冷凍機油及び冷凍機用作動流体組成物
JP6262035B2 (ja) * 2014-03-14 2018-01-17 Ｊｘｔｇエネルギー株式会社 冷凍機油及び冷凍機用作動流体組成物
JP6519909B2 (ja) * 2014-07-18 2019-05-29 出光興産株式会社 冷凍機油組成物、及び冷凍装置
JP5666052B1 (ja) * 2014-07-29 2015-02-12 Ｊｘ日鉱日石エネルギー株式会社 冷凍機油及び冷凍機用作動流体組成物
JP6192851B2 (ja) * 2014-10-16 2017-09-06 三菱電機株式会社 冷凍サイクル装置
JP6495318B2 (ja) * 2014-11-04 2019-04-03 Ｊｘｔｇエネルギー株式会社 冷凍機油及び冷凍機用作動流体組成物
KR102309659B1 (ko) 2015-03-02 2021-10-08 에네오스 가부시키가이샤 냉동기유 및 냉동기용 작동 유체 조성물
CN105176650A (zh) * 2015-10-20 2015-12-23 中国石油化工股份有限公司 一种螺杆式空气压缩机油组合物及其制备方法
FR3056222B1 (fr) * 2016-09-19 2020-01-10 Arkema France Composition a base de 1-chloro-3,3,3-trifluoropropene
CN111801406B (zh) * 2018-03-06 2022-06-21 瑞孚化工有限公司 包含聚亚烷基二醇的润滑剂和制冷剂组合物及其用途
JP2020139072A (ja) * 2019-02-28 2020-09-03 出光興産株式会社 冷凍機用組成物
CN110170077B (zh) * 2019-03-26 2021-09-28 南京理工大学 一种聚离子型生物润滑剂及其制备方法

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WO2016080149A1 (fr) * 2014-11-19 2016-05-26 出光興産株式会社 Composition lubrifiante pour machines frigorifiques et machine frigorifique
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US20160053154A1 (en) 2016-02-25
CN103108944B (zh) 2015-12-16
KR20130124300A (ko) 2013-11-13
TW201219558A (en) 2012-05-16
EP2623583A1 (fr) 2013-08-07
JP2012072273A (ja) 2012-04-12
US10774252B2 (en) 2020-09-15
EP2623583A4 (fr) 2014-05-07
JP5759696B2 (ja) 2015-08-05
US20130274163A1 (en) 2013-10-17
KR101837222B1 (ko) 2018-03-09
EP2623583B1 (fr) 2018-04-04

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